[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2023235534A1 - Composés d'alkylétain de haute pureté et leurs procédés de fabrication - Google Patents

Composés d'alkylétain de haute pureté et leurs procédés de fabrication Download PDF

Info

Publication number
WO2023235534A1
WO2023235534A1 PCT/US2023/024227 US2023024227W WO2023235534A1 WO 2023235534 A1 WO2023235534 A1 WO 2023235534A1 US 2023024227 W US2023024227 W US 2023024227W WO 2023235534 A1 WO2023235534 A1 WO 2023235534A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
formula
tin
compound
solvent
Prior art date
Application number
PCT/US2023/024227
Other languages
English (en)
Inventor
Li Yang
Yuta Hioki
Original Assignee
Gelest, Inc.
Mitsubishi Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gelest, Inc., Mitsubishi Chemical Corporation filed Critical Gelest, Inc.
Publication of WO2023235534A1 publication Critical patent/WO2023235534A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2284—Compounds with one or more Sn-N linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • C07F7/2296—Purification, stabilisation, isolation

Definitions

  • organotin compounds have been shown to be useful in the deposition of tin oxide hydroxide coatings in applications such as extreme ultraviolet (EUV) lithography techniques.
  • EUV extreme ultraviolet
  • alkyl tin compounds provide radiation sensitive Sn-C bonds that can be used to pattern structures lithographically.
  • Dialkyl tin impurities R 2 Sn(NMe 2 ) 2 , where R is an alkyl group, are the source of off-gassing after vapor phase deposition or spin-on coating processes due to the oxostannate cluster films being less dense when the film contains dialkyl groups.
  • R 2 Sn(NMe 2 ) 2 R is an alkyl group
  • the preparation of monoalkyl tin triamide compounds may be accomplished by two different known synthetic pathways.
  • the alkyl group contains a primary and/or a secondary moiety, such as methyl tri(dimethylamino)tin (MeSn(NMe 2 ) 3 ) or isopropyl tri(dimethylamino)tin (iPrSn(NMe 2 ) 3 )
  • the synthesis may be performed using lithium dimethylamide and alkyl tin trichloride (amination) according to the method of Lorberth (Journal of Organometallic Chemistry, 16(2), 235-48 (1969)); see also Jones and Lappert (Organometal. Chem. Rev:, 1, 67 (1966)), as shown in scheme (III).
  • this reaction typically produces significant amounts of dialkyl tin and other tin impurities.
  • the alkyl group contains a tertiary alkyl moiety, such as tert-butyl tris(dimethylamino)tin (t-BuSn(NMe 2 ) 3 )
  • the compounds must be synthesized using an alkylating reagent to convert tin tetraamides by controlling the stoichiometry according to the method reported by Hanssgen et al. (Journal of Organometallic Chemistry, 293(2), 191-5 (1985)), as shown in scheme (IV).
  • the alkyl group in the monoalkyltin triamide compound is a tertiary alkyl group such as t-BuSnCl 3
  • Hanssgen et al. also reports that this compound decomposes rapidly at room temperature, yielding SnCl 2 and t-BuCl. Therefore, tertiary monoalkyl tin triamide compounds cannot be prepared by synthesis with lithium dimethylamide and alkyl tin trichloride.
  • Distillation is a well-developed technology for separating materials in a mixture based on their relative volatility. The exact embodiment of the distillation process depends on the properties, the composition, and the amount of the mixture to be separated. Distillation can and has been used to reduce metallic contamination in multitudes of materials, including organometallic compounds.
  • U.S. Patent Application Publication No. 2019/0337969 describes organometallic tin compounds which have low concentrations of metallic impurities as a result of a multistage distillation process which is compared to processes typically used for sea water desalination.
  • 2020/0239498 describes the purification of monoalkyl tin trialkoxides and monoalkyl tin triamides using fractional distillation and/or ultrafiltration for the removal of metal impurities and fine particulates. The removal of metallic impurities from similar compounds is also described in U.S. Patent Application Publication No. 2020/0241413.
  • U.S. Patent No. 10,787,466 and U.S. PatentNo. 10,732,505 describe organotin hydroxide, alkoxide, and amide compounds having low purity
  • extremely low levels of impurity have only been demonstrated for t-butyl analogs.
  • U.S. Patent No. 8,901,335 describes the purification of a long list of organometallic compounds using a stripping column and a gas stream; the more volatile impurities relative to the organometallic compound are removed and the metallic impurity contents are reduced to specified levels.
  • U.S. Patent No. 11,156,915 relates to the purification of actinic ray- or radiation-sensitive compounds, including tin compounds, using filtration to remove particulates.
  • U.S. Patent No. 5,274,149 teaches a process for making alkyl arsine compounds which includes a distillation step, and which are taught to contain substantially no metallic or oxygenating impurities.
  • a monoalkyl tin triamide compound having formula (1) and having a purity of at least about 99 mol%:
  • R A is a primary alkyl group having about 1 to 10 carbon atoms and R B is a secondary alkyl group having about 3 to 10 carbon atoms; and each R 2 is independently an alkyl group having about 1 to 10 carbon atoms; the method comprising:
  • R 1 Sn(NR 2 2 ) 3 (1) wherein R 1 is selected from R A R B and R c ;
  • R A is a primary alkyl group having about 1 to 10 carbon atoms
  • R B is a secondary alkyl group having about 3 to 10 carbon atoms
  • R c is a tertiary alkyl group having about 3 to 10 carbon atoms
  • each R 2 is independently an alkyl group having about 1 to 10 carbon atoms
  • the method comprising storing the sample of the monoalkyltin triamide compound having formula (1) without light exposure and at a temperature of less than about 30°C.
  • Embodiment 1 A monoalkyl tin triamide compound having formula (1) and having a purity of at least about 99 mol%:
  • R 1 Sn(NR 2 2 ) 3 (1) wherein R 1 is selected from R A R B and R c ;
  • R A is a primary alkyl group having about 1 to 10 carbon atoms
  • R B is a secondary alkyl group having about 3 to 10 carbon atoms
  • R c is a tertiary alkyl group having about 3 to 10 carbon atoms
  • each R 2 is independently an alkyl group having about 1 to 10 carbon atoms
  • a content of R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ) is less than about 1 mol%.
  • Embodiment 2 The monoalkyl tin triamide compound according to Embodiment 1, wherein a content of dialkyl bis(dialkylamino) tin having formula (2) is less than about 1 mol%.
  • Embodiment 3 The monoalkyl tin triamide compound according to Embodiment 1 or 2, wherein a total content of tetrakis(dialkylamino)tin is less than about 1 mol%.
  • Embodiment 4 The monoalkyl tin triamide compound according to any of the preceding Embodiments, wherein a content of tetraalkyl tin is less than about 1 mol%.
  • Embodiment 5 The monoalkyl tin triamide compound according to any of the preceding Embodiments, wherein the color is substantially colorless.
  • Embodiment 6 The monoalkyl tin triamide compound according to Embodiment 5, wherein an APHA is less than about 20.
  • Embodiment 7 The monoalkyl tin triamide compound according to any of the preceding Embodiments, wherein R 1 is an isopropyl group, R 2 is a methyl group, and the compound has formula (3):
  • Embodiment 8 The monoalkyl tin triamide compound according to Embodiment 7, wherein a content of diisopropylbis(dimethylamino) tin is less than about 1 mol%.
  • Embodiment 9 The monoalkyl tin triamide compound according to Embodiment 8, wherein a total content of tetrakis(dimethylamino)tin is less than about 1 mol%.
  • Embodiment 10 The monoalkyl tin triamide compound according to any of the preceding Embodiments, wherein the content of R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ) is less than about 0.05 mol%.
  • Embodiment 11 A method of synthesizing a monoalkyl tin triamide compound having formula (1a) and having a purity of at least about 85 mol%:
  • R 1 Sn(NR 2 2 ) 3 (1a) wherein R 1 is selected from R A and R B ; R A is a primary alkyl group having about 1 to 10 carbon atoms and R B is a secondary alkyl group having about 3 to 10 carbon atoms; and each R 2 is independently an alkyl group having about 1 to 10 carbon atoms; the method comprising:
  • Embodiment 12 The method according to Embodiment 11, wherein the compound having formula (1a) has a purity of at least about 99 mol%.
  • Embodiment 13 The method according to Embodiment 11 or 12, wherein the compound having formula (1a) contains less than about 1 mol% R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ).
  • Embodiment 14 The method according to Embodiment 13, wherein the compound having formula (1a) contains less than about 0.05 mol% R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ).
  • Embodiment 15 The method according to any of Embodiments 11-14, wherein step (b) is performed at about -78°C to 40°C.
  • Embodiment 16 The method according to Embodiment 15, wherein step (b) is performed at about 0°C to about 10°C.
  • Embodiment 17 The method according to any of Embodiments 11-16, wherein the first solvent and the second solvent are each independently selected from the group consisting of a hydrocarbon solvent, an aromatic solvent, and an ether solvent.
  • Embodiment 18 The method according to any of Embodiments 11-17, wherein steps (a) to (d) are performed substantially without light exposure.
  • Embodiment 19 The method according to any of Embodiments 11-18, wherein steps (a) and (b) are performed in a stainless steel vessel.
  • Embodiment 20 The method according to Embodiment 11, further comprising distilling the compound having formula (1a).
  • Embodiment 21 The method according to Embodiment 20, wherein the distillation comprises distilling the crude product having formula (1a) at about 1 torr, discarding any distillate before the boiling point of the monoalkyl triamide having formula (1a), and collecting the distillate obtained at the boiling point of the monoalkyltin triamide having formula (1a) to yield a product containing at least about 99 mol% monoalkyl tin triamide having formula (1a).
  • Embodiment 22 The method according to Embodiment 20 or 21, comprising performing a fractional distillation using an operating pressure of about 0.1 to 50 torr and a pot temperature of about 50 to 120°C, wherein the purified monoalkyl tin triamide compound having formula (1a) contains less than about 0.1 mol% of a dialkyl bis(dialkylamino)tin compound having formula (2).
  • Embodiment 23 The method according to any of Embodiments 20 to 22, comprising performing the distillation substantially without light exposure.
  • Embodiment 24 The method according to any of Embodiments 20 to 23, comprising performing the distillation using a condenser temperature within about 1-10°C of the dew point of the monoalkyl tin triamide compound having formula (1a) at the operating pressure and at a reflux ratio of about 10 to 100.
  • Embodiment 25 The method according to any of Embodiments 20 to 24, wherein the distillation is performed using a stainless steel column packed with a stainless steel packing material.
  • Embodiment 26 The method according to any of Embodiments 20 to 25, wherein the distillation is performed a light-shielded apparatus comprising glass.
  • Embodiments 27 A method of storing a sample of a monoalkyl tin triamide compound having formula (1) and having a purity of at least about 99 mol%:
  • R 1 Sn(NR 2 2 ) 3 (1) wherein R 1 is selected from R A R B and R c ;
  • R A is a primary alkyl group having about 1 to 10 carbon atoms
  • R B is a secondary alkyl group having about 3 to 10 carbon atoms
  • R c is a tertiary alkyl group having about 3 to 10 carbon atoms
  • each R 2 is independently an alkyl group having about 1 to 10 carbon atoms
  • the method comprising storing the sample of the monoalkyltin triamide compound having formula (1) substantively without light exposure and at a temperature of less than about 30°C.
  • Embodiment 28 The method according to Embodiment 27, wherein the sample of the monoalkyl tin triamide compound having formula (1) is stored for about three days to about one year.
  • Embodiment 29 The method according to Embodiment 27 or 28, wherein the sample of the monoalkyltin triamide undergoes substantively no decomposition after a storage time of about three days to about one year.
  • Embodiment 30 The method according to any of Embodiments 27 to 29, wherein a content of R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ) in the sample of the monoalkyl tin triamide having formula (1) is less than about 1 mol%.
  • Embodiment 31 The method according to Embodiment 30, wherein the content of R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ) in the sample of the monoalkyl tin triamide having formula (1) is less than about 0.05 mol%.
  • Embodiment 32 The monoalkyl tin triamide compound having formula (1) according to any of Embodiments 1 to 10, wherein R 1 is selected from R A and R B and the compound is produced by a method comprising: (a) lithiating a solution comprising a dimethylamine and a first solvent to produce a lithium dimethylamide solution having a concentration of up to about 10 wt %;
  • Embodiment 33 The method according to Embodiment 32, wherein step (b) is performed at about -78°C to about 40°C.
  • Embodiment 34 The method according to Embodiment 33, wherein step (b) is performed at about 0°C to about 10°C.
  • Embodiment 35 The method according to any of Embodiments 32-34, wherein the first solvent and the second solvent are each independently selected from the group consisting of a hydrocarbon solvent, an aromatic solvent, and an ether solvent.
  • Embodiment 36 The method according to any of Embodiments 32-35, wherein steps (a) to (d) are performed substantially without light exposure.
  • Embodiment 37 The method according to any of Embodiments 32-36, wherein steps (a) and (b) are performed in a stainless steel vessel.
  • Embodiment 38 The method according to any of Embodiments 32-37, further comprising distilling the compound having formula (1).
  • Fig 1 is a graph depicting the boiling points of iPrSn(NMe 2 ) 3 (A) and iPr 2 Sn(NMe 2 ) 2 (B) at different pressures;
  • Fig. 2 is a graph depicting the photodecomposition of 1 PrSn(NMe 2 ) 3 over time;
  • Fig. 3 is a 119 Sn NMR (neat) spectrum depicting the formation of iPrSn(NMe 2 ) 2 (NMeCH 2 NMe 2 );
  • Fig. 4 is a 1 H NMR (C 6 D 6 ) spectrum of methyl tris(dimethylamino)tin;
  • Fig. 5 is a 119 Sn NMR (neat) spectrum of methyl tris(dimethylamino)tin;
  • Fig 6 is a 1 H NMR (C 6 D 6 ) spectrum of isopropyl tris(dimethylamino)tin;
  • Fig. 7 is a 119 Sn NMR (neat) spectrum of isopropyl tris(dimethylamino)tin;
  • Fig. 8 is a 119 Sn NMR (neat) spectrum of isopropyl tris(dimethylamino)tin synthesized in THF solution;
  • Fig. 9 is a 119 Sn NMR (neat) spectrum of isopropyl tris(dimethylamino)tin synthesized at about 0°C;
  • Fig. 10 is a 119 Sn NMR (neat) spectrum of isopropyl tris(dimethylamino)tin synthesized at about -40°C;
  • Fig. 11 is a 119 Sn NMR (neat) spectrum of isopropyl tris(dimethylamino)tin synthesized at about -78°C.
  • monoalkyl tin triamide compounds represented by formula (1) and having a purity of at least about 99 mol%.
  • the compounds having formula (1) contain no more than about 1 mol% dialkyl bis(dialkylamino) tin compounds having formula (2) relative to the total amount of tin.
  • R 1 is selected from R A R B and R c .
  • R A is a primary alkyl group having about 1 to 10 carbon atoms, preferably about 1 to about 5 carbon atoms, including methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc.; preferred are methyl or ethyl groups.
  • R B is a secondary alkyl (linear alkyl or cycloalkyl) group having about 3 to 10 carbon atoms, more preferably about 3 to about 5 carbon atoms, such as, without limitation, isopropyl, isobutyl, sec- butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, isopentyl, sec-pentyl, etc.; presently preferred are isopropyl and cyclopentyl groups.
  • R c is a tertiary alkyl group having about 3 to 10 carbon atoms such as tert-pentyl, 3-ethyl 3-pentyl, methyl 3-pentyl, methylcyclopentyl, methylcyclohexyl and the preferred t-butyl.
  • Each R 2 is independently an alkyl group having about 1 to 10 carbon atoms, preferably about 1 to 5 carbon atoms, including methyl, ethyl, propyl, butyl, pentyl, etc.; preferred are methyl or ethyl groups.
  • a total content of R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ), also referred to herein as compound (4), is preferably less than about 1 mol%, preferably even lower as described below. Further, the content of the compound having formula (2) is preferably less than about 1 mol%, preferably even lower as described below.
  • the contents of the compounds having formulas (4) and (2) are each independently preferably less than about 0.9 mol%, less than about 0.8 mol %, less than about 0.7 mol %, less than about 0.6 mol %, less than about 0.5 mol %, less than about 0.4 mol %, less than about 0.3 mol %, less than about 0.2 mol %, less than about 0.1 mol %, less than about 0.05 mol %, less than about 0.04 mol %, less than about 0.03 mol %, less than about 0.02 mol %, less than about 0.01 mol %, or non-detectable by 119 Sn NMR, that is, the compounds having formulas (4) and (2) are in some embodiments undetectable in a sample of the compound having formula (1).
  • the content of the compounds having formula (2) is too high, it reduces the cross- linking and toughness when the material is used for EUV lithography resists. Furthermore, the compound having formula (2) can cause outgassing when the photoresists are illuminated by extreme ultraviolet radiation which can lead to degradation of the very expensive multilayer- coated optics in extreme situations.
  • the dialkyl tin impurity level it is possible to reduce the dialkyl tin impurity level to as low as a level which is undetectable by 119 Sn NMR by employing carefully controlled reaction and distillation conditions.
  • the impurity limit to less than about 0.3 mol%, more preferably less than about 0.1 mol% based on stable production and economic consideration.
  • R’ is an isopropyl group
  • R 2 is a methyl group
  • the compound having formula (1) is (iPr)Sn(NMe 2 ) 3 (formula (3)), in which the dialkyl tin impurity is (iPr) 2 Sn(NMe 2 ) 2 .
  • the compound when the compound has formula (3), it has a purity of at least about 99 mol% and contains no more than about 1 mol% (iPr) 2 Sn(NMe 2 ) 2 .
  • the content of tetrakis(dialkylamino)tin (such as tetrakis(dimethylamino tin) in the monoalkyl tin triamide compounds having formula (1) is less than about 1 mol%. In some embodiments, the content of tetraalkyl tin in the monoalkyl tin triamide compounds having formula (1) (such as tetrakis(isopropyl)tin in (iPr)Sn(NMe 2 ) 3 as described above) is less than about 1 mol%.
  • tetrakis(dialkylamino)tin and tetraalkyl tin are each independently preferably less than about 0.9 mol%, less than about 0.8 mol %, less than about 0.7 mol %, less than about 0.6 mol %, less than about 0.5 mol %, less than about 0.4 mol %, less than about 0.3 mol %, less than about 0.2 mol %, less than about 0.1 mol %, less than about 0.05 mol %, less than about 0.04 mol %, less than about 0.03 mol %, less than about 0.02 mol %, less than about 0.01 mol %, or non-detectable by 119 Sn NMR, that is, these compounds are undetectable in the sample of the compound having formula
  • a total content of R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ), also referred to herein as compound (4) is less than about 1 mol%, and may be a compound having formula R A Sn(NMe 2 ) 2 (NMeCH 2 NMe 2 ) or R B (NMe 2 ) 2 (NMeCH 2 NMe 2 ).
  • the content of the compounds having formula (4) or (5) is preferably less than about 1 mol%, less than bout 0.9 mol %, less than about 0.8 mol%, less than about 0.7 mol%, less than about 0.6 mol %, less than about 0.5 mol%, less than about 0.4 mol %, more preferably less than about 0.3 mol%, even more preferably less than about 0.2 mol%, less than about 0.1 mol%, less than about 0.05 mol%, etc.
  • the level of the compound having formula (4) or (5) it is possible to reduce the level of the compound having formula (4) or (5) to as low as less than about 0.1 mol%, such as less than about 0.05 mol%, by employing carefully controlled reaction and distillation conditions.
  • the impurity limit it is often practical to control the impurity limit to less than about 0.3 mol%, preferably less than about 0.1 mol%, based on stable production and economic considerations.
  • the monoalkyl tin triamide compounds having formula (1) are substantially colorless.
  • the monoalkyl tin triamide compounds having formula (1) have APHA color of less than about 20.
  • the APHA color of a composition containing tin compounds may be controlled (such as by minimizing the formation of colored impurities) during distillation such as by using light-shielding or appropriate distillation apparatuses, as described below.
  • APHA color also referred to as the Hazen or Platinum/Cobalt (Pt/Co) scale
  • Pt/Co Platinum/Cobalt
  • the APHA color scale ranges from 0 to 500, where 1 APHA color is equal to 1 ppm of Pt/Co.
  • APHA color can be assessed through visual comparison of standards or with a spectrophotometer, as described in ASTM D1209-05 (2019).
  • the organometallic tin compounds having formula (1) may be used for the formation of high-resolution EUV lithography patterning precursors and are attractive due to their high purity and minimized concentrations of dialkyl impurities having formula (2), as well as additional impurities as set forth above.
  • aspects of the disclosure additionally relate to methods for synthesizing the high purity alkyl tin compounds having formula (1) described above which are suitable for use in the microelectronic industry.
  • These high purity compounds may be substantially free of dialkyl tin compounds having formula (2) and/or impurities having formula (4) or (5), have desired color levels, and may be prepared without multi-stage distillation or, in some embodiments, without any purification.
  • the term “high purity” may be understood to mean a purity greater than about 99 mol%, more preferably greater than about 99.1 mol %, greater than about 99.2 mol%, greater than about 99.3 mol%, greater than about 99.4 mol %, greater than about 99.5 mol %, greater than about 99.6 mol %, greater than about 99.7 mol %, greater than about 99.8 mol %, greater than about 99.9 mol %, greater than about 99.95 mol%, greater than about 99.98 mol%, greater than about 99.99 mol%, or even higher.
  • substantially free may be understood to mean that the impurity is not detectable by 119 Sn NMR, which can have detection limits as low as 0.3 mol%, 0.1 mol%, 0.05 mol%, or 0.04 mol% (depending on the particular compound or impurity) when testing the sample using specific conditions without dilution in deuterated solvent, such as by using more than 2,000 scans.
  • the detection limit is 0.01mol%.
  • 119 Sn NMR spectroscopy is ideally suited to the quantitative analysis of monoalkyl tin compounds due to its high sensitivity to small structural changes and large spectral range of 6500 ppm (see Davies et al., Eds.; Tin Chemistry: Fundamentals. Frontiers, and Applications; Wiley (2008)). This allows for easy identification and quantification of monoalkyl tin compounds and their impurities because 119 Sn resonances are highly resolved. 119 Sn NMR suffers from reduced sensitivity compared to other analytical methods such as GC, HPLC, or 1 H NMR .
  • monoalkyl tin compounds are analyzed without dilution, and a large number of spectral acquisitions (at least 2000, preferably more than 10,000 for unknown impurity detection) are acquired to measure the low levels of impurities described in this work.
  • detection limits of 0.01 mol% dialkyl tin diamides and other Sn compounds such as compounds having formulas (2), (4), and (5) can be achieved.
  • the detection limit is 0.3 mol % because the peak is broad.
  • methods for preparing the monoalkyl tin triamide compounds according to aspects of the disclosure involves the following general steps, each of which is described below: 1 . lithiating a solution of dimethylamine and a first solvent to produce lithium dimethylamide;
  • reaction conditions and parameters such as solvent, relative amounts of reactants, stirring conditions, temperature, and concentrations should be carefully controlled to ensure the production of the desired compound in high purity.
  • the first and second solvents are not particularly limited, but preferred solvents include hydrocarbons (such as, but not limited to, hexane, hexanes, heptane, and cyclohexane), aromatics (such as, but not limited to, toluene and xylene), and ethers (such as, but not limited to, THF and Et2O), and mixtures thereof. Particularly presently preferred are hydrocarbons and aromatics as the main component of the solvent for removing LiCl by filtration. Toluene and hexane are presently the most preferred solvents for easy removal of the product under vacuum at low temperature following the reaction.
  • hydrocarbons such as, but not limited to, hexane, hexanes, heptane, and cyclohexane
  • aromatics such as, but not limited to, toluene and xylene
  • ethers such as, but not limited to, THF and Et2O
  • ethers such as the most preferred THF, are presently preferred solvents because of the high solubility of lithium dimethylamide in these types of solvents. It is also within the scope of the disclosure to use mixtures of these solvents. In some embodiments, the solvent used for the lithiation step and the solvent used for the amination step are the same.
  • the preferred amount of lithium dimethylamide relative to the alkyl trichlorotin is greater than about 3.0 equivalents, greater than about 3.05 equivalents, greater than about 3.09 equivalents, greater than about 3.10 equivalents, or greater than about 3.15 equivalents. If the amount of lithium dimethylamide is too low, the reaction speed will be too low and the amount of impurities will increase due to side reactions such as redistribution.
  • the stirring speed during the addition of the alkyl trichlorotin is significant in determining the purity of the resulting product.
  • a solution of lithium amide in hexane or toluene is in fact a heavy slurry, so stirring at a high speed is preferable for sufficient mixing.
  • stirring at too high a speed can cause problems with the motor due to the heavy slurry.
  • the preferred stirring speed is more than about 10 rpm, more than about 20 rpm, more than about 40 rpm, more preferably more than about 60 rpm and most preferably more than about 100 rpm.
  • the preferred stirring speed is less than about 500 rpm, less than about 400 rpm, less than about 300 rpm, more preferably less than about 250 rpm and most preferably less than about 200 rpm.
  • appropriate stirring blades include paddle blades, anchor blades, Twinstir blades, ribbon blades, 3 -blade retreat impellers, and log bone blades.
  • it is important to have high blade peripheral speed because miniaturization and lithium amide slurry and high reactivity are high shear stress achieved in blade peripheral speed (blade tip speed, m/s).
  • the preferred blade peripheral speed is about 0.1 rpm or more, preferably 0.3 rpm or more, most preferably 0.5 rpm or more and 1000 rpm or less, preferably 100 rpm or less, most preferably 50 rpm or less.
  • the blade peripheral speed is calculated by the following formula (a):
  • Blade peripheral speed (m/s) ⁇ x D x N/60 (a)
  • D represents blade diameter (m) and N represents the number of rotations (rpm).
  • the lower preferred temperature is about -78°C, about -40°C, about -20°C, about -10°C, or the most preferred lower temperature of about 0°C
  • the upper limit of the temperature is about 40°C, about 20°C, or the most preferred upper limit of about 10°C.
  • the preferred temperature range is about 0°C to about 10°C. Tf the reaction temperature for the lithiation is too low, the reaction viscosity may be too high. Conversely, if the reaction temperature is too high, the HNNte will evaporate.
  • the lower preferred temperatures are about -78°C, about -40°C , about -20°C, about -10°C , most preferably about 0°C and the upper limit of the temperature is about 40°C, about 25°C, about 20°C, or the most preferred upper limit of about 10°C.
  • the preferred temperature range is about 0°C to about 10°C.
  • the reaction is preferably performed at room temperature. If the temperature is too low, the reaction rate will be too slow, whereas if the temperature is too high, byproducts will be produced.
  • the lithium dimethylamine is presently present in the solution in an amount of up to about 30wt%, more preferably up to about 20 wt%, up to about 15 wt%, or up to about 10 wt %. It has been found that this dilute concentration provides an effective slurry for solid and liquid reactions. On the other hand, the productivity is lower in dilute condition in industrial conditions.
  • R 1 Sn(NR 2 2 ) 3 (1a) involves the following steps, each of which is described in further detail below:
  • R 1 is selected from R A andR B ;
  • R A is a primary alkyl group having about 1 to 10 carbon atoms and
  • R B is a secondary alkyl group having about 3 to 10 carbon atoms; and
  • each R 2 is independently an alkyl group having about 1 to 10 carbon atoms.
  • the method steps (a) to (d) are performed substantially without light exposure, such as performing at least steps (a) and (b) in an amber or stainless-steel reactor.
  • Light exposure as explained below, has detrimental effects on the monoalkyl tin triamide compounds.
  • the first solvent and the second solvent are the same.
  • the first step in the method involves lithiating dimethylamine in a solution of a first solvent such as hexanes in an amount of up to (but not greater than) 10 wt %. It has been found that this dilute concentration provides an effective slurry for solid and liquid reactions.
  • the lithiation is performed at a preferred temperature of about -10°C to about 10°C, and at about 0°C to about 10°C in some embodiments.
  • the lithiation may be performed with n-BuLi or other common lithiating reagents commonly used in the art, such as t-BuLi or HexylLi.
  • Such lithiating agents are commonly employed in a hexanes solution and additional hexanes may be added so that the lithium dimethylamide is present in the desired concentration range. Excess dimethylamine is required to ensure that the lithiating reagent is fully reacted.
  • the reaction is performed under an inert atmosphere, such as nitrogen or argon, and the addition rate is controlled to limit the exothermic reaction. Following the completion of the addition, the reaction mixture is warmed to room temperature to vaporize the butane byproduct and excess dimethylamine, then cooled to about -10°C to about 10°C, or to at about 0°C to about 10°C in some embodiments.
  • an alkyl trichlorotin solution in a second solvent such as toluene is added to the reaction mixture which is maintained at a preferred temperature of about - 10°C to about 10°C, or at about 0°C to about 10°C in some embodiments.
  • the alkyl trichlorotin is added such that the amount of lithium dimethyl amide is in an amount of at least about 3.09 equivalents relative to the amount of alkyl trichlorotin.
  • the alkyl trichlorotin solution is preferably added in a dropwise fashion to control the exothermic reaction.
  • the second method step is preferably performed in an inert atmosphere, such as nitrogen or argon.
  • reaction mixture After completing the addition of alkyl trichlorotin to the reaction mixture, the reaction mixture is allowed to slowly warm to room temperature, such as over a period of about four hours, and then stirred for an additional time period at room temperature, such as for about four hours.
  • the reaction mixture is then filtered, such as through sparkler, to remove the LiCl byproduct. Other means of filtration which are known in the art may also be employed.
  • the resulting salt is then rinsed, such as with anhydrous hexanes, and the solvents (such as hexanes and toluene) are removed under reduced pressure by means known in the art to produce a crude product containing at least about 85 mol% monoalkyl tin triamide.
  • the crude product having formula (1a) is distilled such as at about 1 torr, such as by using a 300 mm Pro-Pak column, discarding any distillate before the boiling point of the monoalkyl tin triamide, and collecting only the distillate obtained at the boiling point of the monoalkyl tin triamide to yield a product containing at least about 99 mol% monoalkyl tin triamide having formula (1a).
  • the boiling points of two representative monoalkyl tin triamides are shown in Table 1. As an example, if the desired product is methyl tin triamide, distillates obtained at lower than 34°C are discarded, and only distillates obtained at 34-35°C are collected.
  • the distillate obtained at the boiling point, such as 34-35 °C for methyl tin triamide, contains the monoalkyl tin triamide compound having a purity of at least about 99 mol%.
  • the desired compound having formula (1a) is methyl tin triamide
  • the 119 Sn NMR (neat) spectrum showing peaks at ⁇ -16.78 (99.5%) and ⁇ 5623 (0.5%) agrees with published data for methyl tin triamide and dimethyl tin diamide, respectively.
  • the compound having formula (1 a) contains less than about 1 mol% R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ) or less than about 0.05 mol% R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ).
  • a further aspect of the disclosure relates to a method of synthesizing a monoalkyl tin triamide compound having formula (1) and having a purity of at least about 85 mol%:
  • R 1 Sn(NR 2 2 ) 3 (1) wherein R 1 is selected from R A and R B
  • R A is a primary alkyl group having about 1 to 10 carbon atoms
  • R B is a secondary alkyl group having about 3 to 10 carbon atoms
  • each R 2 is independently an alkyl group having about 1 to 10 carbon atoms
  • One method for preparing an isopropyl tin triamide compound having formula (3) according to aspects of the disclosure involves the following steps:
  • a second method for preparing an isopropyl tin triamide compound having formula (3) according to aspects of the disclosure involves the following steps:
  • the processes for producing the isopropyl tin triamide compound having formula (3) are the same as that described above for producing a monoalkyl tin triamide compound having formula (1) except that no distillation step may be is required, that is, the product obtained after step (b) is already at least about 99 mol% pure.
  • the methods described above for synthesizing the isopropyl tin triamide compound having formula (3) may also be employed to synthesize other alkyl tin triamide compounds having formula (1) with only the alkyl tri chlorotin reactant varied.
  • Isopropyl tin triamide produced by the methods according to the disclosure are substantially colorless liquids with 119 Sn NMR (neat) spectra showing peaks at ⁇ -64.85 (99.8%) and 8 - 19.06 ppm (0.2%), agreeing with published and collected data for isopropyl tin triamide and diisopropyl tin diamide respectfully.
  • the product may be further distilled to remove any undesired organic impurities and/or byproducts, as well as to isolate any photo decomposed byproduct.
  • the low temperature has been found to slow the substitution reaction, which increases the risk of comproportionation
  • light or heat can accelerate the comproportionation and form up to 15 mol% dialkyl tin amides as determined by 119 Sn NMR.
  • the amination reaction is performed as a solid slurry in hexanes and is a liquid reaction.
  • the lithium dimethylamide must be prepared properly.
  • the concentration of reactants is diluted, such as by employing lithium dimethylamide in a hexane slurry at a concentration of not more than about 10 wt %.
  • comproportionation may be minimized by performing the reaction at preferred temperatures of around -10°C to 10°C or about 0°C to about 10°C rather than at a lower temperature.
  • THF may be employed instead of hexanes to form a homogeneous solution of lithium dimethylamide.
  • iPrSn(NMe 2 ) 3 can be produced at very high purity (containing no more than about 0.05 mol% dialkyl tin compounds and other specified impurities) without purification in a pilot scale.
  • Methods of purification encompassed by the disclosure include:
  • the size of the alkyl group (and its similarity in size with the NMe 2 group) can affect the boiling point differences between monoalkyl tin triamides and dialkyl tin diamides, and fractional distillation is typically the superior method to isolate the contaminants.
  • the difference between the molecular weights of 1 PrSn(NMe 2 ) 3 (A) and 1 Pr2Sn(NMe 2 ) 2 (B) is small (294 g/mol and 293 g/mol, respectively).
  • the triamido tin compound is lighter than the diamido tin compound by only 13 g/mol.
  • the difference in the boiling points of compounds A and B can be extremely small.
  • the boiling points of these two compounds having purities of > 97 mol% were measured over a wide range of pressures, as shown in Fig. 1. It may be seen that the boiling point difference between the two compounds is within 2 °C in the pressure range of 0.7-10 torr.
  • the boiling points of t BuSn(NMe 2 ) 3 and t Bu2Sn(NMe 2 ) 2 at 0.4 torr are 50 °C (measured) and 90 °C (reported in Chemische Berichte , 112(8), 2798-803 (1979)), respectively. Accordingly, purification by fractional distillation is challenging and requires specific distillation parameters which have been specifically developed.
  • the difference in mass between the alkyl group and the amido group is large, (for example, the tBu-NMe 2 pair has a difference of 13 amu), purification by fractional distillation is expected to be less difficult. When the difference is small, the purification is expected to be more difficult.
  • the iPr-NMe 2 pair has a difference of -1 amu (i.e., the iPr group is slightly lighter than the amido group).
  • the cyclohexyl - NMe 2 pair has a molecular weight difference of 39 amu and the cycloheptyl - NMe 2 pair has a molecular weight difference of 53 amu. Schwarzenbach et al.
  • a further aspect of the disclosure relates to a method of using fractional distillation to purify 1 PrSn(NMe 2 ) 3 having an initial purity of at least about 85 mol%, and even a purity of at least about 97 mol% or at least about 99 mol%.
  • the method comprises performing a fractional distillation using an operating pressure of about 0.1 to about 50 torr (such as greater than about 0.1 torr, greater than about 0.2 torr, greater than about 0.3 torr, preferably greater than about 0.5 torr, more preferably greater than about 1 torr, preferably less than about 50 torr, less than about 30 torr, less than about 20 torr, less than about 10 torr, most preferably about 1 torr). If the pressure is too high, the formation of decomposition and redistribution products is accelerated. If the pressure is too low, volatilization speed is too high and separation efficiency through the distillation column is too low.
  • the fractional distillation preferably employs a pot temperature of about 50°C to about 120°C (preferably greater than about 50°C, greater than about 60°C, preferably greater than about 70°C, preferably greater than about 80°C, preferably greater than about 90°C, preferably greater than about 100°C, most preferably greater than about 105°C and preferably less than about 120°C, preferably less than about 115°C, most preferably about 110°C). If the pot temperature is too low, the volatilization speed is too low and the distillation time is too long. Conversely, if the pot temperature is too high, decomposition of the product is accelerated.
  • the fraction distillation preferably employs a condenser temperature within about 10°C, more preferably within about 7°C, more preferably within about 5°C, more preferably within about 3 °C, most preferably within about 1°C of the dew point of the desired compound having formula (1) such as iPrSn(NMe 2 ) 3 at the employed operating pressure and a reflux ratio of about 10 to 100 (preferably about 20 to 80, more preferably about 40 to 60, more preferably about 50), thereby obtaining a sample of iPrSn(NMe 2 ) 3 having a purity of greater than about 99.5 mol%.
  • a condenser temperature within about 10°C, more preferably within about 7°C, more preferably within about 5°C, more preferably within about 3 °C, most preferably within about 1°C of the dew point of the desired compound having formula (1) such as iPrSn(NMe 2 ) 3 at the employed operating pressure and a reflux ratio of about 10 to 100 (preferably about 20 to 80
  • the purified sample of iPrSn(NMe 2 ) 3 contains less than about 0.1 mol% (iPr) 2 Sn(NMe 2 ) 2 as determined by known analytical methods, such as GC and HPLC or is even undetectable by 119 Sn NMR.
  • one method of purification of 1 PrSn(NMe 2 ) 3 employs fractional distillation using a pot temperature below about 112°C to avoid the formation of the tetramethyl ami do tin compound Sn(NMe 2 )4 and the removal of substantial amounts of the dialkyl tin compound (iPr) 2 Sn(NMe 2 ) 2 .
  • the following conditions may be employed in the fractional distillation purification method of i PrSn(NMe 2 ) 3 according to aspects of the disclosure: 10 torr pressure, 105°C pot temperature, 95°C condenser temperature, and a reflux ratio of 50.
  • 10 torr pressure 105°C pot temperature
  • 95°C condenser temperature 105°C pot temperature
  • a reflux ratio of 50 105°C condenser temperature
  • Monoalkyl tin triamide compounds can undergo disproportionation to the dialkyl tin diamide and the tetraamide compounds.
  • the degree of disproportionation is affected by the temperature in the distillation pot, with higher temperatures expected to lead to higher degrees of disproportionation.
  • the disproportion activation energy is related to the size of the alkyl group (R). For example, when R is a methyl group, disproportion can be observed around 45 °C. As another example, when R is an isopropyl group, the disproportionation occurs around 110 °C. Disproportion of the tert-butyl group occurs at higher temperatures.
  • the two impurities resulting from disproportionating the mono-alkyl tin tri-amide compounds differ in molecular weight from the starting mono-alkyl compound in accordance with the difference between the masses of the alkyl and amido groups.
  • One product will be heavier than the starting mono-alkyl tin tri-amide and the other product will be lighter than the mono-alkyl tin tri-amide. Consequently, the lighter compound is expected to appear in the distillate fraction and the heavier compound to appear in the bottom fraction from the distillation, guaranteeing both a light and a heavy impurity and making the distillation more difficult.
  • the 119 Sn NMR depicting the formation of the compound having formula (5) is shown in Fig. 3.
  • the rate of photodecomposition is increased with increasing temperature. Accordingly, maintaining the purified samples of iPrSn(NMe 2 ) 3 in the dark (without light exposure) minimizes the formation of undesirable light-induced decomposition byproducts and making it possible to provide (iPr)Sn(NMe 2 ) 3 in which a total content of substances having a chemical shift in the 119 Sn NMR spectrum of around -84 ppm in is less than 1% by mass.
  • Light control during the reaction steps to produce the monoalkyl tin triamide compounds is also important and may be accomplished by employing amber or stainless-steel reactors or glass reactors which are shielded from light.
  • the distillation may be performed using a stainless steel column packed with a stainless steel packing material.
  • the distillation may be performed in a light-shielded apparatus comprising glass such as glass equipment, glass-lined equipment, glass- coated equipment, etc. Shielding may be accomplished by any method known in the art such as, for example, employing light-shielded containers such as amber glass, metal (SUS) containers, wrapping the container with a light-shielding cover such as cloth, foil or film, using light- shielding coatings, or performing the distillation in a dark room.
  • light-shielded containers such as amber glass, metal (SUS) containers
  • SUS metal
  • a method of storing a sample (such as, but not limited to a sample of more than about 0.5 kg) of a monoalkyl tin triamide compound having formula (1) and having a purity of at least about 99 mol% comprises storing the sample of the monoalkyltin triamide compound having formula (1) substantially without light exposure and at a temperature of less than about 30°C.
  • the sample of the compound having formula (1) may have a content of R 1 Sn(NR 2 2 ) 2 (N(R 2 )CH 2 NR 2 2 ) of less than about 1 mol% or less than about 0.05 mol%.
  • the sample of the monoalkyl tin triamide compound having formula (1) may be stored for about three days to about one year, such as about a week or longer, not more than about ten months, a period of about two to six weeks, and all intermediate times as desired.
  • the sample is stored at a temperature of less than about 30°C, less than about 25°C, less than about 20°C, and preferably greater than about -10°C.
  • “Substantively without light exposure” may be understood to mean that the sample is protected from light exposure to the greatest possible extent, such as by storage in an amber or stainless steel vessel.
  • the sample of the monoalkyltin triamide undergoes substantively no decomposition after a storage time of about three days to about one year as described above.
  • Example 1 Column design and general operations
  • the tetra-amido Sn(NMe 2 ) 4 impurity (6) is formed from the disproportionation of (iPr)Sn(NMe 2 ) 3 , co-producing the already present di-alkyl (iPr) 2 Sn(NMe 2 ) 2 impurity (7).
  • the effect becomes noticeable as the pot temperature increases from 110°C to 115°C.
  • (iPr)Sn(NMe 2 ) 3 has a FW of 294.0. With both a light and a heavy impurity, the desired (iPr)Sn(NMe 2 ) 3 compound becomes a middle product. A batch distillation process would then require a forecut to remove the tetra- impurity. Continuous distillation would require two columns to recover the (iPr)Sn(NMe 2 ) 3 .
  • compositions measured in the system as shown in the following Tables 3 and 4 show the effect of increasing pot temperature on the degree of purification achieved.
  • the tin compounds (3), (6), and (7) have the structures shown above.
  • the reaction mixture was fdtered through sparkler to remove the LiCl byproduct.
  • the salt was rinsed with anhydrous hexanes (2 x 500 mL).
  • the solvent was removed under reduced pressure.
  • the residue was distilled under reduced pressure (49-53°C, 0.5 torr) with a 316 SS Pro-Pak column equipped with an amber distill head.
  • the product was collected in an amber glass receiver as a clear colorless liquid. Yield: 803g (73.3%).
  • the reaction mixture was fdtered through sparkler to remove the LiCl byproduct.
  • the salt was rinsed with anhydrous hexanes (2 x 100 mL).
  • the solvent was removed under reduced pressure.
  • the relative amounts of the desired product (3) and the biproduct (7) are shown in Table 5 and the 119 Sn NMR spectra for the reactions at about 0°C, about -40°C, and about -78°C shown in Figs. 9, 10, and 11, respectively. It may be seen that the highest purities were obtained at about -78°C and about 0 °C and that the lowest purity was obtained at about -40 °C. Further, from among the three temperatures studied, the ideal temperature for the reaction is about 0 °C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des composés de triamide d'étain monoalkylique ayant une pureté d'au moins environ 99 % en moles et une formule chimique RSn(NMe2)3. R1 est sélectionné parmi RA, RB et RC; RA est un groupe alkyle primaire ayant environ de 1 à 10 atomes de carbone, RB est un groupe alkyle secondaire ayant environ de 3 à 10 atomes de carbone, et RC est un groupe alkyle tertiaire ayant environ de 3 à 10 atomes de carbone; chaque R2 est indépendamment un groupe alkyle ayant environ de 1 à 10 atomes de carbone; et une teneur en R1Sn(NR2 2)2(N(R2)CH2NR2 2) est inférieure à environ 1 % en moles. L'invention concerne également des procédés de synthèse, de purification et de stockage de ces composés. Les composés de monoalkyl étain peuvent être utilisés pour la formation de précurseurs de formation de motifs de lithographie EUV à haute résolution et sont attractifs en raison de leur pureté élevée et de la concentration minimale de dialkyl étain et d'autres impuretés d'étain.
PCT/US2023/024227 2022-06-02 2023-06-02 Composés d'alkylétain de haute pureté et leurs procédés de fabrication WO2023235534A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202263348173P 2022-06-02 2022-06-02
US63/348,173 2022-06-02

Publications (1)

Publication Number Publication Date
WO2023235534A1 true WO2023235534A1 (fr) 2023-12-07

Family

ID=87070982

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2023/024227 WO2023235534A1 (fr) 2022-06-02 2023-06-02 Composés d'alkylétain de haute pureté et leurs procédés de fabrication

Country Status (3)

Country Link
US (2) US20230391804A1 (fr)
TW (1) TW202406920A (fr)
WO (1) WO2023235534A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12060377B2 (en) 2022-08-12 2024-08-13 Gelest, Inc. High purity tin compounds containing unsaturated substituent and method for preparation thereof
WO2024181551A1 (fr) * 2023-03-02 2024-09-06 三菱ケミカル株式会社 Composé d'étain de haute pureté, son procédé de stockage et de production, et produit d'hydrolyse d'étain, solution de produit d'hydrolyse d'étain et couche mince de produit d'hydrolyse d'étain l'utilisant
US12145955B2 (en) 2023-09-27 2024-11-19 Gelest, Inc. Cyclic azastannane and cyclic oxostannane compounds and methods for preparation thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11697660B2 (en) * 2021-01-29 2023-07-11 Entegris, Inc. Process for preparing organotin compounds
WO2023235534A1 (fr) * 2022-06-02 2023-12-07 Gelest, Inc. Composés d'alkylétain de haute pureté et leurs procédés de fabrication
CN117718003B (zh) * 2023-12-13 2024-11-08 合肥安德科铭半导体科技有限公司 用于去除有机胺基锡中金属杂质的吸附剂及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5274149A (en) 1991-07-11 1993-12-28 American Cyanamid Company Process for making alkyl arsine compounds
US8901335B2 (en) 2011-07-13 2014-12-02 Dow Global Technologies Llc Organometallic compound purification and apparatus
US20190337969A1 (en) 2017-08-02 2019-11-07 Seastar Chemicals Inc. Organometallic compounds and methods for the deposition of high purity tin oxide
US20200239498A1 (en) 2019-01-30 2020-07-30 Inpria Corporation Monoalkyl tin trialkoxides and/or monoalkyl tin triamides with particulate contamination and corresponding methods
US20200241413A1 (en) 2019-01-30 2020-07-30 Inpria Corporation Monoalkyl tin trialkoxides and/or monoalkyl tin triamides with low metal contamination and/or particulate contamination, and corresponding methods
US10732505B1 (en) 2015-10-13 2020-08-04 Inpria Corporation Organotin oxide hydroxide patterning compositions, precursors, and patterning
US10787466B2 (en) 2018-04-11 2020-09-29 Inpria Corporation Monoalkyl tin compounds with low polyalkyl contamination, their compositions and methods
KR20210103950A (ko) * 2020-02-13 2021-08-24 더 보잉 컴파니 멀티 시스템 다중 대역 안테나 및 안테나 어레이 어셈블리
US11156915B2 (en) 2016-03-24 2021-10-26 Fujifilm Corporation Actinic ray-sensitive or radiation-sensitive composition, method for purifying actinic ray-sensitive or radiation-sensitive composition, pattern forming method, and method for manufacturing electronic device
WO2022165381A1 (fr) * 2021-01-29 2022-08-04 Entegris, Inc. Procédé de préparation de composés d'organo-étain

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102625156B1 (ko) * 2021-06-17 2024-01-15 주식회사 이지티엠 박막 증착을 위한 유기 주석 화합물 및 이를 이용한 주석 함유 박막의 형성 방법
WO2023235534A1 (fr) * 2022-06-02 2023-12-07 Gelest, Inc. Composés d'alkylétain de haute pureté et leurs procédés de fabrication

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5274149A (en) 1991-07-11 1993-12-28 American Cyanamid Company Process for making alkyl arsine compounds
US8901335B2 (en) 2011-07-13 2014-12-02 Dow Global Technologies Llc Organometallic compound purification and apparatus
US10732505B1 (en) 2015-10-13 2020-08-04 Inpria Corporation Organotin oxide hydroxide patterning compositions, precursors, and patterning
US11156915B2 (en) 2016-03-24 2021-10-26 Fujifilm Corporation Actinic ray-sensitive or radiation-sensitive composition, method for purifying actinic ray-sensitive or radiation-sensitive composition, pattern forming method, and method for manufacturing electronic device
US20190337969A1 (en) 2017-08-02 2019-11-07 Seastar Chemicals Inc. Organometallic compounds and methods for the deposition of high purity tin oxide
US10787466B2 (en) 2018-04-11 2020-09-29 Inpria Corporation Monoalkyl tin compounds with low polyalkyl contamination, their compositions and methods
US20200239498A1 (en) 2019-01-30 2020-07-30 Inpria Corporation Monoalkyl tin trialkoxides and/or monoalkyl tin triamides with particulate contamination and corresponding methods
US20200241413A1 (en) 2019-01-30 2020-07-30 Inpria Corporation Monoalkyl tin trialkoxides and/or monoalkyl tin triamides with low metal contamination and/or particulate contamination, and corresponding methods
KR20210103950A (ko) * 2020-02-13 2021-08-24 더 보잉 컴파니 멀티 시스템 다중 대역 안테나 및 안테나 어레이 어셈블리
WO2022165381A1 (fr) * 2021-01-29 2022-08-04 Entegris, Inc. Procédé de préparation de composés d'organo-étain

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
"Tin Chemistry: Fundamentals, Frontiers, and Applications", 2008, WILEY
CHEMISCHE BERICHTE, vol. 112, no. 8, 1979, pages 2798 - 803
HANSSGEN ET AL., JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 293, no. 2, 1985, pages 191 - 5
J. MED. CHEM., vol. 57, no. 22, 2014, pages 9220 - 9231
JONESLAPPERT, ORGANOMETAL. CHEM. REV., vol. 1, 1966, pages 67
LORBERTH J. ET AL: "EVIDENCE FOR Sn-N x-BONDING: DIPOLE MOMENTS OF AMINOSTANNANES", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 19, no. 1, 9 June 1969 (1969-06-09), pages 203 - 206, XP093084450, DOI: 10.1016/S0022-328X(00)87771-2 *
LORBERTH, JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 16, no. 2, 1969, pages 235 - 48
SCHWARZENBACH ET AL., ENVIRONMENTAL ORGANIC CHEMISTRY, 1993, pages 56 - 75

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12060377B2 (en) 2022-08-12 2024-08-13 Gelest, Inc. High purity tin compounds containing unsaturated substituent and method for preparation thereof
WO2024181551A1 (fr) * 2023-03-02 2024-09-06 三菱ケミカル株式会社 Composé d'étain de haute pureté, son procédé de stockage et de production, et produit d'hydrolyse d'étain, solution de produit d'hydrolyse d'étain et couche mince de produit d'hydrolyse d'étain l'utilisant
US12145955B2 (en) 2023-09-27 2024-11-19 Gelest, Inc. Cyclic azastannane and cyclic oxostannane compounds and methods for preparation thereof

Also Published As

Publication number Publication date
TW202406920A (zh) 2024-02-16
US20230391804A1 (en) 2023-12-07
US20240092811A1 (en) 2024-03-21

Similar Documents

Publication Publication Date Title
US20240092811A1 (en) High purity alkyl tin compounds and manufacturing methods thereof
KR102560231B1 (ko) 낮은 폴리알킬 오염물을 갖는 모노알킬 주석 화합물,이의 조성물 및 방법
WO2013065806A1 (fr) Composé de type tris(dialkylamide)aluminium et procédé de production d'un film mince contenant de l'aluminium l'utilisant
EP2359922A1 (fr) Procédé de préparation de composés organométalliques
WO2022165381A1 (fr) Procédé de préparation de composés d'organo-étain
JPH0474282B2 (fr)
US7273943B2 (en) Process for the preparation of high-purity zirconium, hafnium, tantalum and niobium alkoxides
EP1489085B1 (fr) Procede de preparation du alkylgallium a purete eleve
CA2856038C (fr) Preparation de composes gallium de trialkyle ou d'indium de trialkyle
KR20240052029A (ko) Euv-패터닝가능한 필름을 위한 주석(ii) 아미드/알콕시드 전구체
JP7322762B2 (ja) ケチミン構造を有する有機ケイ素化合物の製造方法
TWI662044B (zh) 三烷基鎵化合物之製備及其用途
KR100830529B1 (ko) 고순도 하프늄아미드의 제조방법
US20240158422A1 (en) High purity tin compounds containing unsaturated substituent and method for preparation thereof
US12091374B2 (en) Mono-substituted cyclopentadienes and metal cyclopentadienyl complexes and synthesis methods thereof
JP2024020874A (ja) ジアルキル亜鉛の製造方法およびジアルキル亜鉛
CN113563383A (zh) 一种高纯度三甲基锑的制备方法及其应用
JP3858138B2 (ja) ニオブ、タンタルとリチウムとの液体ダブルアルコキシド及びその製法並びにそれを用いた複合酸化物誘電体薄膜の製法
GB2268489A (en) Process for the preparation of DI-ALKYL compounds of group 2B metals
JPH05310764A (ja) 高純度モノアルキルまたはモノアリ−ルアルシン化合物の製造方法
JPH08325272A (ja) 高純度テトラアルコキシシラン及びその製造方法
JPH01268693A (ja) 有機金属化合物の精製方法
JPH02167290A (ja) トリメチルインジウムの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23736499

Country of ref document: EP

Kind code of ref document: A1